CN105324103A - Nail coatings having enhanced adhesion - Google Patents

Abstract

Adhesion of a composition for nail coatings be improved by addition of a polyhedral oligomeric silsesquioxane (POSS). Nail coating compositions that benefit from the addition of a POSS include enamels, reactive composition such as those containing acrylates, solventless compositions and water-based compositions.

Description

There is the finger paint of the adhesion of enhancing

Prioity claim

This application claims the U.S. Provisional Application No.61/814 submitted on April 22nd, 2013, the priority of 691, is intactly incorporated herein by reference it.

Technical field

The embodiment of present disclosure relates to finger paint (nailcoating).Particularly, present disclosure relates to containing at least one polyhedral oligomeric silsesquioxane (POSS) and has the finger paint compositions of the adhesion of improvement.

Background technology

Nail plate (i.e. natural nail) is formed primarily of keratin, and keratin is water-fast, the fibrous proteins of the principal structural component as skin, hair, animal hair, silk, feather, squama, fingernail and hoof.Although keratin in their aminoacid composition can significant difference very large, hard keratin can fully general with crosslinked polypeptide for feature.Alpha-Keratin such as fingernail and hoof can further with their relatively high amino acid cysteine percentage ratio for feature.Typically, an alpha-helix ball of string for described polypeptide is by means of the disulfide bond crosslinking between adjacent cysteine.Consequent tabular cell is bonded with each other by means of stickum and is kept together by the rivet-like structure being called as desmosome.Many cellular layers are adhered to one another to form nail plate, and it is the structure of similar brick and mortar wall.

The conventional coating for natural nail can divide three classes substantially: nial polish (nailpolish) (also referred to as japanning (lacquer), varnish (varnish) or glaze (enamel)), artificial nails's (also referred to as gel or acrylic resin) and hybrid.The solid constituent that fingernail glaze typically contains multiple dissolving and/or is suspended in non-reactive solvent.Apply and dry time, described deposition of solid on nail surface as transparent, translucent or coloured film.Typically, nial polish is easily scratched, and can easily with removal of solvents (usually in a minute) and if do not remove as described, then can in one to five days from natural nail cracked or peel off.

The surface of fingernail glaze coating nail plate is with there being the glossiness finish (finish) of feature to provide decorative cover finish paint.Fingernail glaze comprises film-forming components usually, this component normally nitrocellulose, cellulose acetate-butyrate or those cellulosic a kind of or whole two kinds with the combination of polyester or other polymer type compounds.Major part nial polish is made up of the nitrocellulose being dissolved in solvent (such as, butyl acetate or ethyl acetate) and or transparent or with various pigment coloring.Typical component can comprise: film former, resin and plasticizer, solvent and coloring agent.

Artificial nails is polymerized to form surface that is hard, toughness on the surface of natural nail.Artificial nails comprises one or more (methyl) acrylate monomers and light trigger or sclerosing agent that can mix immediately before use usually.Optionally, artificial nail composition can comprise solvent liquid state (methyl) acrylate maybe can be used as solvent.This type artificial nails typically with nail plate closely and may irreversibly be combined, and such as must file removal by physical means.

The component that hybrid systems contains film-forming components and can be polymerized.In exemplary hybrid systems, the described component that can be polymerized such as (methyl) acrylate forms 3-dimension (3-D) thermosetting grid (lattice) and described film-forming components such as nitrocellulose or cellulose acetate-butyrate are dispersed in described 3-D network.Compared with the fingernail glaze of routine, described 3-D thermosetting grid provides the durability of enhancing, toughness and resistance to marring, and the film-forming components of dispersion mutually simultaneously provides solubility network to allow the removeability characteristic improved compared to artificial nails.

Apply finger paint to surface, nail plate typically to require to process surface, nail plate.This surface treatment typically relates to the use of priming paint (primer) and/or makes nail plate roughening (such as by means of the use of file).This processing procedure may cause the injury to nail plate, and this is debatable especially for having the individual of thin fingernail.

Priming paint is interface compatibility by improving between surface (such as nail plate and the coating that applies) and improves the adhesion promoter of adhesion.Such as, if the priming paint employed, then the coating (coating) of nial polish can be resisted cracked and peel off.Compared to nial polish, priming paint is more compatible with nail plate.Priming paint serves as " intermediate link " (" go-between ") or " anchor ", to improve adhesion.

Priming paint also often uses, because acrylic compounds nail product has poor adhesion to nail plate usually together with artificial nails's reinforce (enhancement).Usually, nail plate priming paint can be considered to two-sided tape that nail plate is connected with fingernail reinforce.Surface, nail plate is made up of the chemical group with ad hoc structure.Primer composition must interact with nail plate and (methyl) acrylic monomer in described reinforce.Use the priming paint of these types, need to carry out physical abrasion to realize the adhesion to the proper level at the described keratin based end to nail plate.In addition, these priming paint can be destructive, if improper use, then they can cause the injury to nail plate and perienchyma.These priming paint also cause fading of fingernail reinforce.

But for not peeling off or the cracked finger paint existence needs with the adhesion of enhancing not injuring nail surface or make nail surface fade from nail surface in this area.

The aforementioned of association area is described in whole interior description comprising, describe in this article any and all can be the document (comprising any and whole United States Patent (USP)) that the public obtains and be intactly incorporated herein by reference particularly.Never be intended to admit as such to the aforementioned description of association area: any document (comprising the U.S. Patent application of pending trial) wherein described is the prior art of the embodiment of present disclosure.In addition, disclosed embodiment is not intended to limit to the description of any shortcoming relevant to described product, method and/or device herein.In fact, the embodiment of present disclosure can comprise some feature of described product, method and/or device, and there is not the shortcoming that they are described.

Summary of the invention

Finger paint described herein provide described coating to fingernail and/or the adhesion of enhancing between the layer of layered coating.

In an aspect, finger paint compositions comprises at least one polyhedral oligomeric silsesquioxane.

Described finger paint compositions can contain film forming polymer further.Described film forming polymer can be water dispersible, and described compositions can contain water further.Described finger paint compositions can contain non-water, non-reactive solvent further.Described finger paint compositions can contain at least one reactivity (methyl) acrylate further; The polymer non-reacted with at least one, solvent can be dissolved in.

Described finger paint compositions can contain at least one reactivity (methyl) acrylate further; At least one reactive amino formic acid esters (methyl) acrylate; At least one polymethyl methacrylate (PMMA)-polymethylacrylic acid (PMAA) copolymer; The polymer that at least one is non-reacted, can be dissolved in solvent; With at least one non-reactive solvent.Described finger paint compositions can comprise the reactive polypropylene glycol of at least one (methyl) acrylated monomers or Polyethylene Glycol (methyl) acrylated monomers further.

Described finger paint compositions may further include at least one reactivity (methyl) acrylate; With polymerization accelerator, polymerization initiator or its combination; Wherein said compositions is not containing the solvent added.Described finger paint compositions can comprise the monomer containing many carbonyl-ethenyl further.

Described finger paint compositions can contain at least one reactive amino formic acid esters (methyl) acrylate further.Described finger paint compositions can contain at least one polymethyl methacrylate (PMMA)-polymethylacrylic acid (PMAA) copolymer further.Described finger paint compositions is cured as the acrylic compounds thermosets being wherein limited with space when being exposed to actinic radiation.Described finger paint compositions may further include non-reactive solvent.

Described at least one reactivity (methyl) acrylate can comprise Hydroxypropyl methacrylate (HPMA), hydroxyethyl methylacrylate (HEMA), ethyl methacrylate (EMA), tetrahydrofurfuryl methacrylate, pyromellitic acid anhydride two (methyl) acrylate, pyromellitic acid anhydride glyceryl dimethylacrylate, Pyromellitic Acid dimethylacrylate, methyl acryloyloxyethyl isocyanate, 2-HEMA/succinate, 1, 3-glycerine dimethacrylate/succinate adduct, methacrylic acid phthalic acid list ethyl ester, or its mixture.

Described finger paint compositions may further include the reactive polypropylene glycol of at least one (methyl) acrylated monomers or Polyethylene Glycol (methyl) acrylated monomers.

Described finger paint compositions can further containing being selected from following adhesion promoter:

Hydroxypropyl methacrylate (HPMA),

Hydroxyethyl methylacrylate (HEMA),

Ethyl methacrylate (EMA),

Tetrahydrofurfuryl methacrylate (THFMA),

Pyromellitic acid anhydride two (methyl) acrylate,

Pyromellitic acid anhydride glyceryl dimethylacrylate,

Pyromellitic Acid dimethylacrylate,

Methyl acryloyloxyethyl isocyanate,

2-HEMA/succinate,

1,3-glycerine dimethacrylate/succinate adduct,

Methacrylic acid phthalic acid list ethyl ester,

Methyl acryloyloxyethyl isocyanate,

2-HEMA/succinate,

1,3-glycerine dimethacrylate/succinate adduct,

Butyl methacrylate,

Isobutyl methacrylate,

PEG-4 dimethylacrylate,

PPG monomethacrylates,

Trimethylol-propane trimethacrylate,

Isopropylidene diphenyl 2-glycidyl methyl acrylate,

Lauryl methacrylate,

Cyclohexyl methacrylate,

N-Hexyl methacrylate,

Urethane methacrylate,

Triethylene-glycol dimethylacrylate,

Ethylene glycol dimethacrylate,

Tetraethylene-glycol dimethylacrylate,

Trimethylol-propane trimethacrylate,

Neopentylglycol dimethacrylate,

Acetoacetoxy groups methacrylate,

Acetoacetoxyethyl methacrylate (AAEMA),

Polyetheramine,

Glycidyl methacrylate,

Maleic anhydride,

Terpolymer containing vinyl acetate,

Organosilan,

Organic titanate,

Chloridized polyolefin,

Sucrose acetate isobutyrate,

Caprylic/capric triglyceride,

Hydrogenated rosins acid glyceride,

Hydrogenated rosins acid pentaerythritol ester,

Styrene/methyl styrene/indene copolymer,

The isocyanates PVC of end-blocking,

Daiamid PVC, and

Its mixture.

Described at least one polyhedral oligomeric silsesquioxane can comprise glycidyl POSS clathrate compound mixture (cagemixture) (EP0409); Trimethoxy-[2-(7-oxabicyclo [4.1.0]-3-in heptan base) ethyl] silane, (EP0408) of hydrolysis; [3-(trimethoxysilyl) propyl group] aniline (AM0281) of hydrolysis; [(dimethyl (norbornenylethyl) siloxy) dihydroxy]- (NB1038); Vinyl silsesquioxane resin-liquid state (PM1285MV); Acrylo clathrate compound mixture (MA0736); The ethoxylation POSS of methacrylated; The glycidyl POSS of ethoxylation; Or its mixture.

Described finger paint compositions can further containing two-, three-or polyfunctional ethylenic unsaturated reactant.

Described can be dissolved in solvent polymer or film forming polymer can be selected from: cellulose esters, cellulose ethanoate alkylates (cellulose acetate alkylates, celluloseacetatealkylate), cellulose acetate-butyrate, cellulose-acetate propionate, ethyl toluenesulfonamide, adipic acid/fumaric acid/phthalic acid/Tricyclodecane Dimethanol copolymer, adipic acid/neopentyl glycol/trimellitic acid anhydride copolymer, phthalic anhydride/trimellitic anhydride/(second) diol copolymer, poly-ethyl cellulose (many ethyl celluloses), poly-hydroxypropyl cellulose (many hydroxypropyl celluloses), polyethyl acrylate oxide, polylactic acid, nitrocellulose, cellulose esters, with its mixture.

In one aspect of the method, the method improving the adhesion of finger paint comprises and adds at least one polyhedral oligomeric silsesquioxane to described finger paint compositions.

In the process, described finger paint compositions may further include at least one reactivity (methyl) acrylate; The polymer non-reacted with at least one, solvent can be dissolved in.Described finger paint compositions may further include: at least one reactivity (methyl) acrylate; At least one reactive amino formic acid esters (methyl) acrylate; At least one polymethyl methacrylate (PMMA)-polymethylacrylic acid (PMAA) copolymer; The polymer that at least one is non-reacted, can be dissolved in solvent; With at least one non-reactive solvent.Described finger paint compositions may further include the reactive polypropylene glycol of at least one (methyl) acrylated monomers or Polyethylene Glycol (methyl) acrylated monomers.

In the method, described finger paint compositions may further include film forming polymer.Described film forming polymer can be water dispersible, and described compositions may further include water.

Described finger paint compositions can comprise non-water, non-reactive solvent further.Described finger paint compositions may further include: at least one reactivity (methyl) acrylate; Polymerization accelerator, polymerization initiator or its combination; And wherein, described compositions is not containing the solvent added.Described finger paint compositions may further include the monomer containing many carbonyl-ethenyl.

From specific descriptions below, also other aspect of the present invention and advantage will become as those skilled in the art are distinct, show and will describe the preferred embodiment of the present invention in the following specifically describes by means of only the explanation of estimated enforcement optimal mode of the present invention.As will be recognized, the present invention is that can have other with different embodiments, and in the case of without departing from the present invention, its some details can multiple obvious in change.Therefore, described description should be regarded as in itself for illustrative and not restrictive.

Detailed description of the invention

Definition

Unless otherwise defined, all technology used herein and scientific terminology have the identical implication usually understood with those skilled in the art.Although can use in practice of the present invention or test with those methods described herein and material type like or the method that is equal to and material, described hereafter is suitable method and material.All publications mentioned herein, patent application, patent and other list of references are intactly incorporated herein by reference.When contradiction, be as the criterion with this description (comprising definition).In addition, material, method and example are only illustrative and be not intended to as restrictive.From specific descriptions below and claims, other features and advantages of the present invention will be distinct.

For the object of understanding promoting embodiment described herein, by introduction preferred embodiment and specific for use language is described.Term used herein only for describing the object of detailed description of the invention, and is not intended to limit the scope of the invention.When using in whole present disclosure, unless context separately has regulation clearly, otherwise " one (kind) (a, an) " of singulative and " being somebody's turn to do (described) " comprises plural referents.Therefore, such as, mention that " (one) compositions (composition) " comprises multiple such compositions (composition) and single compositions (composition).

Term " fingernail " and " nail surface " mean naturally, the nail surface of keratin protein, or are stained with the natural nail of artificial nails or nail tip (nailtip).That is, the compositions that can be polymerized of the present invention directly can be applied to the keratin protein surface of natural nail or have the nail surface of artificial nails or the nail tip reinforce being labelled to it.

Finger paint

The application describes finger paint.Compared with the fingernail glaze of routine, the finger paint of present embodiment is due to following and have a major advantage: its make can also containing coloured described finger paint can adhere to natural nail reach long wearing (wear) time and do not have the adhesion loss of described coating or other destroy sign.The wearing improved is when realizing without the need to carrying out surface treatment (surfaceprepping) (such as by means of use priming paint or surperficial roughening by slightly making with file or other means) to fingernail.Such as, the finger paint of present embodiment directly can be applied to fingernail.

In some embodiments, can recommend to clean nail surface simply to remove too much dust and/or too much natural oil.The clean of nail surface can be realized by means of a small amount of solvent such as isopropyl alcohol or acetone of using.

According to an aspect, the present invention is monolayer finger paint, its can containing color and show enhancing to the adhesion of nail surface to resist cracked and to peel off.According to an aspect, present disclosure is provided for the priming paint on pretreated nails surface before the applying of finger paint, and described priming paint such as can improve the adhesion of finger paint to nail surface compared with undressed fingernail.According to an aspect; present disclosure provides such finger paint: it is between nail surface and can strengthens outward appearance (such as; by glossiness finish is provided or containing color) or protectiveness surface can be provided other layer between prime coat layer (subcoat, basecoat).According to an aspect, present disclosure provides the color layers of the exposed surface being applied to prime coat layer.According to an aspect, present disclosure provides the protective surface coating (finish paint, topcoat) of the exposed surface being applied to color layers or prime coat layer.

Finger paint of the present invention is by being introduced into the adhesion realizing in the compositions being applied to fingernail strengthening by the polyhedral oligomeric silsesquioxane such as limited further hereinafter.Finger paint of the present invention provides the adhesion to nail surface (comprising natural nail and artificial nails) of enhancing, and when being used in multilayer system, the interlayer adhesion force between each layer.Therefore, described finger paint has longer wearing characteristic, and namely on nail surface, the longer time remains intact harmless.In most of situation, finger paint of the present invention still can easily be removed by using suitable solvent.

Many finger paint systems can show the adhesion of enhancing by introducing polyhedral oligomeric silsesquioxane.There is the finger paint system that can be polymerized among those; The finger paint system of film forming; Based on the finger paint system of water; And liquid-with-powder finger paint system.Be described in more detail hereinafter these finger paint systems each and according to spendable component in the finger paint formula of each system.

Polyhedral oligomeric silsesquioxane or " POSS "

Embodiments of the present invention introduce polyhedral oligomeric (or oligomerization) silsesquioxane (POSS) in finger paint.These compounds are different from other polysiloxanes (organosilicon, silicone) resin by their rigid three-dimensional cage structure.In some embodiments, the POSS used in present embodiment has the three-dimensional basket structure formed by multiple Si subelement and Si-O subelement, and at least one of described subelement has one or more R group.In some embodiments, term " POSS " can refer to the POSS molecule with 8 or less silicon atoms (such as 6,7 or 8), and EPOSS (polyhedral oligomeric (or oligomerization) silsesquioxane of expansion) can be used to refer to the structure of those basket structures had more than 8 silicon atoms.The polyorganosiloxane resin of the described basket structure of all formation can be used in present embodiment.Therefore, unless otherwise directed, term " POSS " refers to POSS or EPOSS molecule, no matter and Si atomic number is how many.

POSS has silica core and reactive functional groups from the teeth outwards and by general formula R SiO _1.5the inorganic material represented.Usually, POSS is nano-scale, but can be larger, and this depends on the quantity of Si and O atom in structure and the substituent group that may exist as other local description herein.Cubic silicon sesquioxyalkane such as eight (dimethyl silane oxygen base) silsesquioxane (R ₈si ₈o ₁₂) by forming as follows: rigidity, crystalline silicon dioxide shape core that can be covalently bound with 8 R group, it is spatially strict difinition (well-defined) (0.5-0.7nm).Discuss the description of possible cage in U.S. Patent No. 5942638, this patent is intactly incorporated herein by reference.Described cage separately can by reactivity part being attached to cage atom by further modification (modification).Depend on substituent group, core accounts for about 5% of cumulative volume and causes highly reinforcing skin effect.The structure of the organic facies between described rigidity, hard particle can systematically change; Existing carefully regulates machinery, optical property to set up the probability of structure-property relationships.Such as, by changing the functionality of R group, multiple functionalized macromonomer can be produced, such as the macromonomer of eight senses, its meeting autohemagglutination or cube copolymerization functionalized with other, with the nano-complex providing length dimension and interfacial interaction to be strictly defined.And by changing the functionality of R group, the physics and chemistry that can strengthen between nail surface and described coating or in multilayer system dope layer interacts, to provide the adhesion of the enhancing observed.

In some embodiments, POSS only refers to those compounds existed with rigidity, " cage " type configuration, and the example is shown in following formula I-V.In some embodiments, POSS only refers to some following structure, such as, as unrestricted example, those shown in formula I, III and IVA: it is called as in this article " complete cage ", in described " complete cage ", all faces of three dimensional structure are complete faces, and all silicon atoms are completely saturated.

In some embodiments, the finger paint of present disclosure does not comprise can such as with other POSS that the trapezoidal configuration of formula VI exists, before in U.S. Patent Application Publication No.2002/0114773 about the polymethylsilsesquioxane being such as called as ResinMK disclosed in cosmetic formulations, this U.S. Patent Application Publication is intactly incorporated herein by reference.As disclosed therein, to the effect that described compound with " cage " (that is, formula I, wherein R ₁-R ₈cH ₃--) and both existence of " trapezoidal " configuration (formula VI).Also it is believed that most of polysiloxane polymer exists with " trapezoidal " configuration (formula VI).Contain with regard to " trapezoidal " configuration with regard to said composition, it is not POSS as described below: use this term for the present invention.

The POSS used in the finger paint of present embodiment can form three-dimensional basket structure.In some embodiments, described POSS has at least 6 Si molecules.In some embodiments, described PSS contains 8 Si atoms.POSS can also comprise and be greater than 8 Si atoms or with containing the mixture of such as 6-12 Si atom or 8-12 Si atom, such as, as the mixture of compound containing 8,10 and 12 Si atoms.(namely there is identical Si and O atomic configuration as single POSS structure, even if other substituent group is different) or as the mixture of compound of Si atom with the different numbers having identical or different R group, Si atomic number can also scope be 6-100 or 6-30, and or 6-20 and finally or 6-16.In some embodiments, at least 4 of Si atom are combined with at least 3 other Si atoms (being called herein " completely saturated ") by oxygen atom.All Si atoms are all combined by other Si atom of oxo bridge and at least one.

As shown in the exemplary of formula I to V and VII to X and non-limiting structure, POSS forms the rigid three-dimensional basket structure with at least two complete faces.This rigid cage structure is different from trapezoidal and other structure (for exemplary trapezium structure, see formula VI) not in position in three directions.Si atom is combined with at least 1 R group separately, and is no more than 3, is no more than 2 or be no more than 1 Si atom and be combined more than 2 R group.Such as, by the POSS molecule shown in formula III, there are 6 saturated Si atoms and 5 complete faces (2 faces by 3 Si atoms being connected via oxo bridge restrained and 3 faces are restrained by 4 the Si atoms connected via oxo bridge).Formula IIB has 4 such saturated Si atoms and 2 complete faces (4 Si atoms all by being connected via oxo bridge are restrained).Formula IIC has 6 saturated Si atoms and 3 complete faces (4 Si atoms all by being connected via oxo bridge are restrained).

There is according to the POSS molecule of some embodiments the complete basket structure of formula I:

Following is also possible: one of the oxo bridge between Si atom in succession or even two fractures or disappearance, and described in the case " POSS " is called as and has " incomplete " basket structure.As limiting examples, consider the rigid three-dimensional basket structure shown in formula IIA-E:

Formula III is complete cage, but is produced by 6 Si atoms.

In formula IVA, the Si atomic number in cage is 10, and in formula IVB, Si atomic number is 10, and in formula IVC, the Si atomic number in cage is 12.At formula IVD and IVE, the Si atomic number in cage or core is 16.

The example of one or more fracture of the oxo bridge wherein between Si atom in succession or " incomplete " basket structure of disappearance has been shown in formula V:

Formula VI (trapezoidal configuration (not being the POSS of according to the present embodiment/disclosure)) can be the monomer be connected with other similar structures tail-tail (end-to-end).In the meaning of presents, it is not rigidity, because it can be folding or bending around each R--Si--O--Si--R axle of molecule.Such motion is impossible in the rigidity 3-D basket structure (no matter being complete or incomplete) of the POSS of present embodiment.Therefore, the molecule of this formula is not POSS.

Also noting, the structure that meet formula II when being called by POSS molecule, there is formula II or when being different from complete cage, being illustrated as " opening ", the face of " disappearance " or " fracture " is only illustrative.When with reference to formula II, understand, any one or two faces or any one or two oxo bridges can be fracture or disappearance.The structure of POSS molecule can be considered to wherein silicon (Si) atom roughly at the box (being prism when at formula III) of the shape of each corner or cage.Other Si atom of each Si atom and at least one is by being connected with the key (being also referred to as " oxo bridge ") of oxygen atom.Preferably, at least 4 of the Si atom in POSS structure are " completely saturated ".As used in this article, if Si atom is combined by three other Si atoms of oxygen atom in cage, be " completely saturated ", shown in I, III and IVA; Most preferably, all Si atoms are all " completely saturated ".When showing for the Si atomic time in formula I, the group of each corner can be identical or different and can be one or more such atoms or group: it comprises silicon, silane, siloxanes, polysiloxanes (organosilicon) or organometallic group and does not limit.POSS used in the present invention can have the rigid three-dimensional basket structure as such as shown in formula I-V and VII-X, and described cage has at least two complete face A.Each Si is combined with at least one R group.In some embodiments, be no more than 1 Si atom and be combined more than 2 R group.In some embodiments, be no more than 2 Si atoms and be combined more than 2 R group.Be no more than 3 Si atoms in some embodiments and be combined more than 2 R group.

In some embodiments, POSS material can through type [RSiO _1.5] _∞represent, wherein ∞ represents molar degree of polymerization and R represents organic substituent (H; Siloxy; Ring-type or linear aliphatic or aromatic group, its can in addition containing reactive functional groups as alcohol, ester, amine, ketone, alkene, ether or halogen root or its can contain fluorinated groups).(homoleptic) that POSS used in the present invention can or all join or assorted (heteroleptic) joined.The R group of equal part system only containing a type, and the R group more than a type is contained in assorted part system.In embodiments, inner caged skeleton is formed primarily of inorganic silicon-oxygen key, and the outside of this nanostructured is covered by reactive and/or non-reacted organo-functional group (R), which ensure that this nanostructured with organic monomer and the polymer compatibility and designability.

POSS composition can be represented by following formula:

For to be all made into point, [(RSiO _1.5) _n] _{∑ #},

To be made into point for assorted, [(RSiO _1.5) _n(R ' SiO1 _1.5) _m] _{∑ #}(wherein R ≠ R'),

For functionalized being assortedly made into point that there is closed basket structure, [(RSiO _1.5) _n(XSiO1 _1.5) _m] _{∑ #}(wherein R group can be identical or not identical).The functionalized assorted POSS composition of joining with the basket structure opened can through type [(RSiO _1.5) _n(RXSiO1 _1.5) _m] _{∑ #}represent.

Illustrate, the POSS all joined of formula III, I, IVA and IVC is denoted respectively as: [(RSiO _1.5) ₆] _{∑ 6}, [(RSiO _1.5) ₆] _{∑ 6}, [(RSiO _1.5) ₈] _{∑ 8}, [(RSiO _1.5) ₁₀] _{∑ 10}, and [(RSiO _1.5) ₁₂] _{∑ 12}.Similarly, the functionalized assorted cage POSS opened joined can have following structure and title:

In structure above all and formula, R is identical or different and can is arbitrary part as other local definition in this article, and X includes but not limited to OH, Cl, Br, I, alkoxyl (OR), acetas (CH ₃cOOR), acid (COOH), ester (COOR), peroxide (peroxy) (OOR), amine (NR ₂), isocyanates (NCO), epoxy, alkene and R.Symbol m and n refers to the stoichiometry of described composition.Symbol ∑ represents that described composition forms nanostructured, and symbol # represents the quantity of the Si atom comprised in described nanostructured.The value of # normally m+n's and, wherein n typically scope be 1-24, and m typically scope be 1-12.It should be noted that ∑ # should not be confused with for determining stoichiometric multiplier, because the overall nanostructural characteristic (also referred to as cage size) of its only description system.

The example making nano-structured chemicals can play the attribute of the strengthening (reinforcing) of 1-10nm and the effect of adhesion promoter comprises: (1) they about the unique size of polymer chain dimensions, (2) their following ability: by polymer chain and polymeric system compatibilized, promotes the incompatibility of nano reinforcement agent (reinforcingagent) and the repulsive force of expulsion to overcome.That is, by the change of the R group in each nanostructured, nano-structured chemicals can be designed to present the preferential affinity/compatibility with various finger paint compositions.Therefore, the factor affecting selectivity nano strengthening comprises the concrete nano-scale of nano-structured chemicals, the distribution of nano-scale and the compatibility between nano-structured chemicals and finger paint system and discordance.

POSS used in the present invention typically " is derived " as having one or more R group containing functional group.Other R group can not comprise functional group, but can change with by such as strengthen with the compatibility of the solvent of finger paint or other component, change POSS size to change the physical characteristic of final coating or to strengthen the dissolubility of POSS in finger paint and carry out modification to POSS.As limiting examples, one or more R group can be alkyl, alkene, alkynes, hydroxyl, mercaptan, ester, acid, ether.In some embodiments, " R group " comprises following one or more and does not limit: hydrogen, methyl, ethyl, propyl group, isobutyl group, iso-octyl, phenyl, cyclohexyl, cyclopenta,--OSi (CH ₃) ₂-CH ₂-CH ₂-(CF ₂) ₅cF ₃,--(CH ₂) ₃sH, N ⁺(CH ₃) ₃, O ^-n ⁺(CH ₃) ₃,--OH,--(CH ₂) _nn ⁺h ₃x ^-, wherein n is 0-30 and X is counter ion counterionsl gegenions,

In some embodiments, R can also be silane or siloxane structure, comprises trapezium structure.Formula X is the limiting examples of the POSS that siloxanes replaces:

(see formula IVD and IVE, substituent group can be other cage structure as previously shown.In such cases, can conceptually this structure be thought as front determined single POSS structure or by the POSS of another POSS structure replacement.

Such as, formula I, III and IVA one of each silicon atom residue key can with as " R " group (R ₁-R ₈) ((R in formula III ₁-R ₆)) the various substituent group that describes in detail or group combine.As used in this article, when there is multiple R group in same POSS molecule, each R group can be identical or different, no matter and be all be expressed as R simply or divide into R ₁, R ₂, R ₃... R _n.In one or two POSS molecule be eliminated of the oxo bridge of some embodiments namely wherein between adjacent silicon molecule shown in formula II, IVB and V, the R group of larger quantity is possible.When adopt there is the POSS of 8 Si atoms time, preferably connect being no more than two and being eliminated of (oxo bridge) between these silicon.But, nearly three such bridges (formula IIE) can be eliminated.More preferably, single oxo bridge is only had to be eliminated (formula IIA).As previously mentioned, one or more can be used in conjunction with other substituent other position can not had by the Si combined completely.When single disappearance face, POSS molecule can comprise other R group R ₉and R ₁₀, its can with R ₁-R ₈identical or different.When lacking 2-3 bridge, POSS molecule can comprise other R group R ₉, R ₁₀, R ₁₁and R ₁₂(taking the circumstances into consideration), its all can be identical or different and can with for R ₁-R ₈determined group is identical or different.

The POSS compound with multiple R group is known in the literature.They are described in a lot of patent, and described patent comprises and limiting as follows and not: U.S. Patent No. 5047492,5389726,5484867,5589562,5750741,5858544,5939576,5942638,6100417,6127557,6207364,6252030,6270561,6277451,6362279 and 6486254.These patents describe in detail the method for multiple manufacture basic POSS basket structure and its multiple derivant (comprising the polymer based on POSS).With regard to these patent identifications with describe with regard to multiple POSS molecule, its derivant and the polymer with the structure of formula I-V and VII-X, they are incorporated herein by reference.The discussion for the manufacture of the technology with this compounds derivative described in these patents is also incorporated herein by reference thus.

Usually, R group (such as, R as illustrated in the drawing ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉, R ₁₀, R ₁₁, and R ₁₂, and other suitable R group arbitrarily) can be identical or different, and can be reactive or non-reacted.They can substitute methyl or H, such as, be hydroxyl (-OH); Alkane derivatives (disappearance hydrogen atom), also referred to as alkyl group (except methyl); (there is one or more double bond) thiazolinyl, also referred to as alkene derivatives, the Si usually in them and POSS or lack H with some other molecule junctions; (having one or more triple bond) alkynyl group, is also referred to as alkynes derivant, the Si usually in them and POSS or lack H with some other molecule junctions; Aromatic yl group (6 carbocyclic rings of benzene or 6 carbocyclic rings condensed of other aromatic derivative such as naphthalene), also referred to as the derivant of aromatic hydrocarbons, the Si usually in them and POSS or lack H with some other molecule junctions; Heteroaryl groups (in ring, comprise one or more the 6-unit or the first aromatic ring of 5-that are different from atom such as N, S or O of carbon, or the structure containing the heteroaromatic rings condensed); Carboxyl groups (does not have the organic acid of OH group, such as CH ₃cO-or C ₆h ₅cO-); Alkoxy base (alkyl group be connected with molecule remainder by oxygen) such as methoxyl group; Ester group; Acid groups; Propylene acid group (ester) group; Acrylic acid alkyl ester group; Oh group; Halogen; Amino group; Alkylamino group; Aminoalkyl groups; Group containing one or more uncle or quaternary nitrogen; Containing the group of organosilicon (silicone); Sulfur-containing group; Epoxy radicals; Azo group; Diazonium groups; Halogen; The cyclic compound of ring-opening polymerisation or ring-opening metathesis polymerization can be experienced.R group can also be monomer or polymer, and wherein POSS is used as the pendency substituent group of described polymer.Provide acrylate and cationic polymer that accommodation property is provided in some embodiments.

Time suitable, these R group can itself be replacements or unsubstituted, saturated or unsaturated, line style or branching arbitrarily.Possible replacement (base) comprises C ₁-C ₃₀alkyl group, C ₁-C ₃₀alkenyl group, C ₁-C ₃₀alkynyl group, C ₆-C ₁₈aromatic yl group, carboxyl groups, alkoxyl or other group, carboxylic group, ester group, propylene acid group (ester) group, acrylic acid alkyl ester group, trihydroxy group, amino group, alkylamino group (comprising list and dialkyl amino group), list and dihydroxyalkyl amino group group, cyano group, aminoalkyl groups, the group containing one or more uncle or quaternary nitrogen, the group containing organosilyl group, sulfur-bearing and/or phosphorus, SO ₂x, SO ₃x (wherein X be H, methyl or ethyl), epoxy radicals and containing the group of epoxy radicals, azo group, diazonium groups, halogen, the cyclic compound of ring-opening polymerisation or ring-opening metathesis polymerization can be experienced.In fact, any group that can be connected to the turning of POSS molecule can be used.

When these R group be the fatty acid of carbon containing or fatty alcohol, aromatics or the group of ring-type time, they generally can containing 6-50 carbon atom and can depending on to group be as one sees fit saturated or undersaturated, replace as described above or unsubstituted and branching or line style.

More particularly, possible R group comprises and limiting as follows and not: oh group, comprises list or polyhydroxy group; Phenol; Alkoxyl; Hydroxy alkyl; Silane; Amino and especially, quaternary ammonium compound; Halogenated silanes; Epoxy radicals; Alkyl-carbonyl; Alkane; Haloalkyl; Halogen; Propylene acid group; Metering system acid group; Sulfur alcohol; Nitrile; Norbornene; The alkyl of branching; Polymer; Silane; Silanol; Styryl and mercaptan.Have in the POSS molecule of formula I single, R ₁can be H, R ₂--OH, R ₃--NH ₂, R ₄--CH ₂cH ₂n ⁺cH ₃(OCH ₂cH ₃) CH ₂cH ₂cH ₃, R ₅--CH ₂cH ₂cHOCH ₂(epoxy radicals), R ₆--OC (CH ₃) ₃, R ₇--OOC (CH ₂) ₁₆cH ₃and R ₈can be Cl.This is hypothesis instance, is only used to illustrate that R group can be derivatized individually separately and is to emphasize various possible replacement (base).

In some embodiments, these POSS molecules be not completely with identical R group replace (such as, be not whole R ₁-R ₆, R ₁-R ₈, R ₁-R ₁₀or R ₁-R ₁₂(and other R group any of being determined by circumstances when the quantity of known Si atom in given POSS molecule and available key) is all methyl, isobutyl group or phenyl).This is particularly preferred for the POSS molecule with formula I structure.In addition, when employing divide the period of the day from 11 p.m. to 1 a.m such as formula the POSS with 8 Si subelements described by I, at least one of R group is the group being different from methyl, particularly when silicones is T resin and even more particularly ResinMK time.

It is further envisioned that can by HybridPlastics under term POSS, 55W.LRunnelsIndustrialDriveHattiesburg, MS39401andMayaterials, Inc.P.O.Box87, the commercial compound series that SouthLyon, Mich.48178-0087 obtain.

In some embodiments, the middle POSS used of the coating (finger paint or nail surface coating) of present embodiment has formula (C ₆h ₁₁o ₂) _n(SiO _1.5) _n, wherein n is 6 (see formula IIIs), 8 (see formula I), 10 (see formula IVA) or 12 (see formula IVC), and C ₆h ₁₁o ₂represent the epoxy radicals with the glycidyl type of following structure:

In some embodiments, the POSS used in the coating of present embodiment has formula (C ₆h ₁₁o ₂) _n(SiO _1.5) _n, wherein n is 8,10,12.In some embodiments, the POSS used in the coating of present embodiment has formula (C ₆h ₁₁o ₂) _n(SiO _1.5) _n, wherein n is 8 or 10.In some embodiments, the POSS used in the coating of present embodiment has formula (C ₆h ₁₁o ₂) _n(SiO _1.5) _n, wherein n is 8.In some embodiments, the POSS used in the coating of present embodiment has formula (C ₆h ₁₁o ₂) _n(SiO _1.5) _nthe mixture of POSS structure, wherein n is 6,8,10 and 12.In some embodiments, the POSS used in the coating of present embodiment has formula (C ₆h ₁₁o ₂) _n(SiO _1.5) _nthe mixture of POSS structure, wherein n is 8,10 and 12.In some embodiments, the POSS used in the coating of present embodiment has formula (C ₆h ₁₁o ₂) _n(SiO _1.5) _nthe mixture of POSS structure, wherein n is 8 and 10.

In some embodiments, described POSS molecule is by least one group or multiple group functionalization.Functional group on polymer and POSS material comprises, but be not limited to, functional organic-such as, hydroxyl, carbamate, acrylate (propylene acid group), vinyl, Si--H, amide, functional acrylate, functionality polyamide, PVK, PVA, PS, PEG, PPG, polysaccharide or modified starch, functionality block copolymer, functional polyesters and polyethers, fluorinated polymer and wax to cause the cross-linking reaction between polymer chain and POSS material, thus provide the character of needs.

POSS of the present invention can by the hydrolysis-condensation reaction preparation of the organic silicon monomer such as RSi (OMe) of trifunctional.The method preparing POSS is described in U.S. Patent No. 8133478 and 6372843, they is intactly incorporated herein by reference.

In some embodiments, POSS used in the coating of present embodiment is EP0409, and it is the mixture of caged or non-cage structure, as such as described in U.S. Patent No. 6716919 and 6927270, they is intactly incorporated herein by reference separately.In some embodiments, in the coating of present embodiment, POSS used is MA0736, EP0408, NB1038, AL0104, AL0125, AL0130, AL0136, CA0295, CA0296, CA0298, EP0402, EP0417, EP0418, EP0419, EP0421, EP0423, EP0430, EP0435, FL0578, FL0583, HA0605, HA0615, HA0635, HA0640, IM0670, IM0673, MA0701, MA0702, MA0703, MA0706, MA0716, MA0717, MA0718, MA0719, MA0734, MA0735, MA0736, MS0802, MS0805, MS0813, MS0814, MS0815, MS0825, MS0830, MS0840, MS0860, MS0865, NI0914, NB1000, NB1010, NB1017, NB1021, NB1022, NB1038, NB1070, OL1118, OL1123, OL1159, OL1160, OL1163, OL1170, PG1190, SH1310, SH1311, SO1400, SO1440, SO1444, SO1450, SO1455, SO1457, SO1458, SO1460, SA1532, SA1533, TH1550, TH1555, AM0285, AM0273, PM1285MV, AM0280, AM0281, AM0282, AM0290, AM0291, AM0292, AM0293, AM0275, AM0265, PG1190, AM0270, or its mixture.

POSS functionalized monomer

POSS functionalized monomer has the inorganic-organic three dimensional structure of the hydridization comprising one or more reactive organo-functional group.Although be called as in this article " monomer ", it should be understood that, the reactive organo-functional group of term comprise can polymerizable groups group or can otherwise with other finger paint component or other POSS interaction of molecules to strengthen the group of the physical property such as adhesion and toughness of finger paint.POSS functionalized monomer can comprise non-reacted organic group and functionalization group, multiple non-reacted organic group and a multiple functionalization group or only comprise functionalization group.Such as, the POSS with 8 R group can contain seven non-reacted organic groups and a functionalization group, six non-reacted organic groups and two functionalization groups, five non-reacted organic groups and three functionalization groups, etc., until the POSS containing eight functionalization groups.Unique functional group can include, but not limited to amine, ester, epoxy radicals, metering system acid group, alkene, silane, styryl and mercaptan.By change functional group (one or more) and non-reacted organic group (one or more), many POSS functionalized monomers can be prepared.While can introducing mono-functional POSS monomer by copolymerization or grafting, multi-functional POSS monomer (POSS namely containing more than one functionalization group) can be utilized as effective cross-linking agent.POSS functionalized monomer reacts similarly with standard organic monomer in polymerization, grafting and cross-linking reaction.Although they react as simple organic monomer, when being incorporated in polymeric material, POSS functionalized monomer gives the significant improvement of conventional plastic in heat, machinery and gas separating property.

POSS polymer and resin

POSS polymer and resin have the inorganic-organic composition of hydridization and can be thermoplasticity or thermosets.As a class material, POSS polymer and resin are by forming as follows: (1) wherein POSS functionalized monomer by copolymerization or the polymer that is grafted on polymer chain, or (2) have the silsesquioxane resin of certain basket structure (such as, see, formula X).POSS polymer and resin can be used as the remarkable succedaneum of traditional material or they can by compounding or solution blending to conventional polymeric materials to strengthen the performance of this base resin.The type of current available POSS polymer and resin includes, but are not limited to polysiloxanes (organic siliconresin, silicone), styrenic, acrylic resin and norborene.

POSS molecule can obtain from HybridPlastics, and comprise based on formula I-IV those and do not limit.Other POSS product can be bought from ALDRICH.Also other be described in U.S. Patent No. 8133478,5047492,5858544 and 2465188, is intactly incorporated herein by reference separately thus by it.

The particularly preferred POSS molecule that can be used for manufacturing coating composition according to the present embodiment comprises: trifluoro (13) cyclopenta-POSS (FL0590); Mercaptopropyi isobutyl group-POSS (TH1550); Mercaptopropyi iso-octyl-POSS (TH1555); Poly-(methyclyloxypropyl iso-octyl POSS-is total to-methyl methacrylate) 60% weight (PM1275.4-60); Poly-(methyclyloxypropyl iso-octyl POSS-is total to-methyl methacrylate) 80% weight (PM1275.4-80); Eight isobutyl group-POSS (MS0825); Octaphenyl-POSS (MS0840); Iso-octyl-POSS clathrate compound mixture, 95% (MS0805); EpoxycyclohexyethylSiOi butylcyclohexyl-POSS (EP0399); Expoxycyclohexyl isobutyl group-POSS (EP0402); Glycidyl POSS clathrate compound mixture (EP0409); Glycidyl cyclohexyl-POSS (EP045); Glycidyl isobutyl-POSS (EP0418); Three-glycidyl butylcyclohexyl-POSS (EP0421); With octa-epoxy cyclohexyldimethyl silicyl-POSS (EP0430); Eight aminophenyl-POSS (AM0280); Eight aminophenyl-POSS (AM0285); Trimethoxy-[2-(7-oxabicyclo [4.1.0]-3-in heptan base) ethyl] silane, (EP0408) of hydrolysis; [3-(trimethoxysilyl) propyl group] aniline (AM0281) of hydrolysis; [(dimethyl (norbornenylethyl) siloxy) dihydroxy]- (NB1038); Vinyl silsesquioxane Shu Zhi – liquid state (PM1285MV); Acrylo clathrate compound mixture (MA0736); With eight TMA-POSS (MS0860).

As shown in the limiting examples in following elaboration, multiple POSS structure can be used in finger paint compositions.In some cases, existing finger paint compositions can be strengthened (such as, being strengthened by showing the adhesion of enhancing) by adding POSS to described compositions.POSS can be selected to be provided one group of desirable physical property to the system be modified and presents the compatibility with concrete finger paint system.Based in the system of solvent, desirably POSS exists with the form can dissolved in related solvents.Such as, in Aquo System, desirably POSS exists with form that can be water-soluble.POSS also should be selected such that it does not react undesirably with other component of finger paint between the storage life and before use.Also should consider POSS whether should with other component reaction of system (such as by copolymerization or other chemical reaction), or POSS be should mainly and nail surface (if applying as monolayer or prime coat layer) interact or interact to promote interlayer adhesion force with other layer.POSS the most desirable for embody rule can determine based on the character needed and substituent group or select.For concrete system, use normal experiment, the organic group (it can give the character such as dissolubility and reactivity of needs) on POSS can be changed or test different POSS molecules to reach optimum POSS.

According to the present invention, finger paint can by adding suitable POSS component or being obtained by the brand-new system of preparation to existing finger paint system.Described finger paint system can be, such as, and monolayer system, such as, glaze only containing film-forming components; The system such as gel or acrylic resin of the monolayer energy photocuring containing the monomer that can be polymerized; Containing the system based on solvent of film-forming components with the component that can be polymerized; Or based on the finger paint of water.Before it applies, add POSS with the amount of about 0.01 % by weight to about 20 % by weight of whole compositions.Such as POSS can exist with the amount from about 0.05 % by weight to about 10 % by weight, from about 0.05 % by weight to about 8 % by weight, from about 0.05 % by weight to about 5 % by weight, from about 1 % by weight to about 10 % by weight, from about 1 % by weight to about 8 % by weight, from about 1 % by weight to about 5 % by weight, from about 2 % by weight to about 10 % by weight, from about 2 % by weight to about 8 % by weight, from about 2 % by weight to about 5 % by weight.POSS can be no more than 20 % by weight, is no more than 15 % by weight, is no more than 10 % by weight, is no more than 8 % by weight, is no more than 5 % by weight, is no more than 2 % by weight, the amount of 1 % by weight or lower that is no more than adds.

POSS can directly join existing formula; As some other components with described system if solvent, film former are as the mixture of cellulosic polymer (such as, cellulose alkylates ester is as cellulose acetate-butyrate or CAB), or the mixture of solvent and other component.Or, POSS can introduced for the preparation of between the normal mixing of finger paint compositions and processing period.

Finger paint

The present invention includes and add POSS to following various finger paint and finger paint system: it finger paint (artificial nails, gel, acrylic resin), hybrid systems and the fingernail priming paint that comprise fingernail glaze, can be polymerized.As mentioned above, POSS be introduced into existing getting the raw materials ready (raw material, stock) or basis (base) system, or as to get the raw materials ready or a part for foundational system is prepared.As used in this article, " foundational system " refers to not containing POSS and is different from the existing finger paint of " prime coat layer " (it refers to the finger paint being directly applied to fingernail before other coating).Describe hereinafter and can be added with POSS to strengthen the various coating systems of adhesion property, is then the description to the various components that can exist in finger paint of the present invention.

The finger paint that can be added with POSS be included in such as following disclosed in those: U.S. Patent No. 8124058,6818207,8399537,8263677,8367742,5985951,5785958,5576509,5965147,5639447,6051242,5130125,5512273,5662891,5720804,4871534,5785958 and 7678321; U.S. Patent Application Publication No.2010/0012263,2005/0065297 and 2007/0286827; PCT application announces No.WO2011/011304, WO2011/031578, WO2011/043880 and WO2011/043879; With submit to 22,13/827483 and 2012 on Augusts of submitting to 14,13/042436,2013 on the March of submitting to 7,12/573640,2011 on the March of submitting to 5,12/573633,2009 on the October of submitting in the U. S. application No.13/846024 submitted on March 18th, 2013, on October 5th, 2009 61/692096.These patents, announcement and patent application disclosure separately is intactly incorporated herein by reference thus.

The type of finger paint

Fingernail glaze

Embodiment of the present invention comprises the fingernail enamel composition for being applied to fingernail, and it is deposited film on fingernail after the solvent evaporates.Fingernail enamel composition be generally have be dissolved in organic solvent as butyl acetate, ethyl acetate, isopropyl alcohol etc., with and composition thereof in the liquid based on polymer of film forming polymer.After being in application to fingernail, solvent evaporates, thus makes film forming component wherein and any pigmentation on the surface of fingernail.

The finger paint (gel, acrylic resin and hybrid) that can be polymerized

Embodiments of the present invention comprise for being applied to fingernail and being polymerized with the compositions that can be polymerized producing finger paint or artificial nails's structure.The described compositions that can be polymerized preferably at room temperature has the anhydrous liquid of half sports gel to the denseness of freely-movable liquid.Before being about to use, the described compositions that can be polymerized is applied to nail surface and is shaped by fingernail technician.After polymerization, obtain artificial nails's structure.

Multilamellar

According to an aspect, coating of the present invention applies as three different layers, and the one or more of described layer can be solidifications at least partly.POSS may reside in any one or more layers of described coating.According to an aspect, the applying of any one of described layer can be omitted.According to an aspect, any two applying of described layer can be omitted.Therefore, consider, described coating can as one deck, two-layer or Three-tider architecture applying.According to an aspect, the formula for color layers is only had to contain coloring agent reagent.According to an aspect, the formula for any described layer can contain coloring agent.

The aspect of present disclosure is provided as the prime coat layer of the layer intermediate between fingernail and coating surface.Prime coat layer of the present invention can be the liquid that can be polymerized, and provides conformal coating on nail surface.Described prime coat layer can also comprise pigment or color.Compositions of the present invention can be polymerized with photochemical radiant energy.Described actinic radiation can be ultraviolet (UV) radiation.In some embodiments, on described prime coat layer, other layer is not applied.

It can be the intermediate layer of decorative layer such as color layers that the aspect of present disclosure provides.Described intermediate layer can be applied to the exposed surface of prime coat layer.

The aspect of present disclosure provides the face coat of the exposed surface being applied to described prime coat layer or intermediate layer.

One or more layers of described finger paint can comprise the component that one or more are selected from the component of following category: reactive monomer and/or oligomer and/or polymer; High molecular (methyl) acrylate polymer or copolymer; Transmit strengthen adhesion and give polymerization grid with the polymer of solvent sensitivity; Urethane methacrylate resin; (methyl) acrylate monomer of the adhesion of improvement, viscosity, wearing and tearing and durability is provided; Can exist the aromatics improving adhesion or aliphatic series (methyl) acrylate monomer; Monomer and/or the oligomer of one or more free hydroxyl radicals are provided; Adhesion promoter; The polymer non-reacted, solvent can be dissolved in; Optional resin; Plasticizer; UV stabilizing agent; Polymerization initiator/light trigger; Polymerization regulator; Coloring agent; And solvent.Describe these categories in more detail hereinafter, and discuss the exemplary compounds of each category.

Based on the glaze of water

Glaze finger paint formula based on water comprises water as solvent and film forming polymer.The described glaze finger paint formula based on water can comprise one or more of the component of following category: (methyl) acrylate copolymer miscible with water; (methyl) acrylate copolymer; Styrene-(methyl) acrylate copolymer; Polyurethane finishing agent and/or thickening agent; Low poly-or polyoxy alkylidene (polyalkylene oxide) (such as, (second) glycol ethers, dipropylene glycol, n-butyl ether dipropylene glycol, PEG or PPG or a diethyl acetal); Nonionic soap; And coloring agent.Glaze based on water does not contain organic solvent such as ethyl acetate, butyl acetate, acetone etc.In some embodiments, glaze finger paint based on water comprises water, styrene-acrylic copolymer (such as, styrene-(methyl) acrylate copolymer) and acrylate copolymer (such as, (methyl) acrylate copolymer).

Liquid-and-power formulations

In some embodiments, the finger paint that can be polymerized is obtained by liquid-and-powder method.Before being about to use, the appropriate finger paint compositions that can be polymerized formed primarily of one or more liquid monomers is poured in plate or other suitable vessel.Brush or other jig for molding are immersed in described compositions to form globule on the end of instrument.Then this pearl is dipped in the polymer powder mixture in independent plate.When the pearl of the liquid monomer on brush is dipped in polymer powder materials, on the end of jig for molding forming surface bulk, adhesion, the particulate material of agglomeration.Or, described powder furnishing in described liquid can be starched to obtain dough-like, and jig for molding is dipped in described dough-like.Usually, the ratio of 0.2 to 1.3 parts of polymer powder foot couples, 1 part of liquid monomer will provide suitable polymerization.The finger paint compositions that can be polymerized of described liquid state is softening and partly dissolve described powder.The end of described forming tool when its load has dough-like then for nail type that carve on nail surface (moulding goes out) is new.Polymerization initiator in described powder (such as, peroxide) and described liquid monomer in polymerization accelerator (such as, amine) combined effect is with the polymerization of catalysis monomer composition to obtain artificial nails's structure, and then it be shaped and polishing as required.Desirable machinability is presented in order to make the described compositions that can be polymerized, described compositions should make, when by the compositions that can be polymerized and above-mentioned powder catalyst respectively 1 to 0.5 mixture when mixing and preserve for 15 DEG C, described mixture should 400 to 1400 seconds, preferably 600 to 1200 seconds, most preferably 800 to 1000 seconds inner gels to 100, the viscosity of 000 centipoise.Liquid-and-powder composition and method are described in such as U.S. Patent No. 6818207, it are intactly incorporated herein by reference.

Described liquid monomer compositions can containing one or more ethylenically unsaturated monomers as one or more (methyl) acrylate monomers.It optionally can also comprise the monomer containing many carbonyl-ethenyl; Plasticizer; Polymerization accelerator; UV absorbent; Polymerization regulator.Such monomer composition is described in U.S. Patent No. 6818207, it is intactly incorporated herein by reference.

Suitable polymer powder preferably containing at least some olefinic degree of unsaturation to allow the polymer that is cross-linked or copolymer.Described polymer powder mixture is generally by forming as follows: line style particulate through chain elongation (chain extension) or crosslinked acrylate or methacrylate polymers, and it can be random or block copolymer form.The most typically, described acrylate or methacrylate polymers are one or more combinations of ethyl methacrylate or methyl methacrylate or ethyl acrylate or methyl acrylate or these polymer.More commonly, the copolymer of ethyl methacrylate and methyl methacrylate is used.Described polymer powder compositions can also comprise polymerization accelerator or catalyst, and this catalyst is designed to work together with the accelerator found in the described compositions that can be polymerized.Most preferably peroxide, as benzoyl peroxide.Described polymer powder can also comprise other batching (ingredient) as titanium dioxide and other dyestuff and/or pigment.

Described monomer composition can contain 0.001-5%, preferably 0.001-4% or the more preferably polymerization accelerator of 0.005-3% weight or catalyst, and it is preferably aromatics or aliphatic tertiary amine.Suitable aliphatic series or aromatic uncle amine are included in C.T.F.A.CosmeticIngredientDictionaryandHandbook, SeventhEdition, the 1532-1534 page of 1997 is set forth those, the document is incorporated herein by reference thus.Preferably aromatic uncle amine is as N, N-bis-(C _1-6) alkyl-p-toluidine is as N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine; Or N, N-bis-(C _1-6) alkyl benzene amine is as Ν, Ν-dimethylaniline.Preferred accelerator is N, N-dimethyl-p-toluidine.The chain elongation of the monomer of described amine polymerization accelerator in described monomer composition and/or crosslinked in play the effect of catalyst.In liquid/powder systems wherein by described can in the compositions of the polymerization situation of being polymerized by chemical means, the accelerator the most often used is the amine as mentioned above combined as benzoyl peroxide with organic peroxide.Usually, described amine accelerator is present in described monomer composition, and peroxide is present in described powdered composition, and described powdered composition and described monomer composition mix to cause being polymerized, immediately said composition is applied ester fingernail afterwards, as discussed above.

The component used in finger paint of the present invention

Reactive monomer and/or oligomer and/or polymer

A kind of embodiment of described fluid composition compositions comprised to polymerization provides the reactive monomer of the adhesion of increase and/or oligomer and/or polymer.In some embodiments, such reactive monomer and/or oligomer and/or polymer can comprise ethylenic unsaturated reactant such as (methyl) acrylate.Known to the technical staff in polymer arts, term (methyl) acrylate contains acrylate and/or methacrylate.According to an aspect, such reactive monomer, and/or oligomer, and/or polymer can be selected from as follows: Hydroxypropyl methacrylate (HPMA), hydroxyethyl methylacrylate (HEMA), EMA, THFMA, pyromellitic acid anhydride two (methyl) acrylate, pyromellitic acid anhydride glyceryl dimethylacrylate, Pyromellitic Acid dimethylacrylate, methyl acryloyloxyethyl isocyanate, 2-HEMA/succinate, 1, 3-glycerine dimethacrylate/succinate adduct, methacrylic acid phthalic acid list ethyl ester, with its mixture.According to an aspect, such reactive monomer and/or oligomer and/or polymer can have acidic functionality.According to an aspect, the compositions to polymerization provides the described monomer of the adhesion of increase, oligomer or polymer to exist with about 0-about 50 % by weight.

Described ethylenic unsaturated reactant can be about can the olefinic bonds of addition polymerization be single-, two-, three-or multi-functional.Multiple ethylenic unsaturated reactant is suitable, as long as described reactant can be polymerized the artificial nails's structure producing polymerization when being exposed to suitable stimulation.Suitable ethylenic unsaturated reactant is open in U.S. Patent No. 6818207, this patent is incorporated herein by reference.

High molecular (methyl) acrylate polymer or copolymer

According to some embodiments, the finger paint of present embodiment can also comprise high molecular (methyl) acrylate polymer or copolymer.Although the compositions of present embodiment can comprise acrylate, methacrylate is preferred, because compared with acrylate formulations, methacrylate is more impossible causes sensitization of skin.Term as used in this article " (methyl) acrylate " means methacrylate, acrylate or its mixture.

In some embodiments, described high molecular (methyl) acrylate polymer or copolymer are the copolymers of alkyl methacrylate (AMA) and methacrylic acid (MAA).Described alkyl group can be such as methyl, ethyl, propyl group or butyl.According to an aspect, described monomer is present in described polymer the ratio (AMA/MAA of 90:10) of 10 parts of MAA with 90 parts of AMA.According to an aspect, MAA monomer fraction can from 0 to 100% change, and namely described (methyl) acrylate polymer or copolymer can be methacrylate polymer.According to an aspect, described AMA-MAA copolymer has the AMA:MAA monomer ratio of about 50:50.According to an aspect, described AMA-MAA copolymer has the AMA:MAA monomer ratio of about 60:40.According to an aspect, described AMA-MAA copolymer has the AMA:MAA monomer ratio of about 80:20.According to an aspect, described AMA-MAA copolymer has the AMA:MAA monomer ratio of about 90:10.According to an aspect, described AMA-MAA copolymer has the AMA:MAA monomer ratio of about 95:5.

In some embodiments, described high molecular (methyl) acrylate polymer or copolymer are the copolymers of methyl methacrylate (MMA) and methacrylic acid (MAA).According to an aspect, described monomer is present in described polymer the ratio (MMA:MAA of 90:10) of 10 parts of MAA with 90 parts of MMA.According to an aspect, MAA monomer fraction can from 0 to 100% change, and namely described (methyl) acrylate polymer or copolymer can be methyl methacrylate polymer.According to an aspect, described MMA-MAA copolymer has the MMA:MAA monomer ratio of about 50:50.According to an aspect, described MMA-MAA copolymer has the MMA:MAA monomer ratio of about 60:40.According to an aspect, described MMA-MAA copolymer has the MMA:MAA monomer ratio of about 80:20.According to an aspect, described MMA-MAA copolymer has the MMA:MAA monomer ratio of about 90:10.According to an aspect, described MMA-MAA copolymer has the MMA:MAA monomer ratio of about 95:5.

In some embodiments, described high molecular (methyl) acrylate polymer or copolymer are the copolymers of butyl methacrylate (BMA) and methacrylic acid (MAA).According to an aspect, described monomer is present in described polymer the ratio (BMA:MAA of 90:10) of 10 parts of MAA with 90 parts of BMA.According to an aspect, MAA monomer fraction can from 0 to 100% change, and namely described (methyl) acrylate polymer or copolymer can be butyl methacrylate polymers.According to an aspect, described BMA-MAA copolymer has the BMA:MAA monomer ratio of about 50:50.According to an aspect, described BMA-MAA copolymer has the BMA:MAA monomer ratio of about 60:40.According to an aspect, described BMA-MAA copolymer has the BMA:MAA monomer ratio of about 80:20.According to an aspect, described BMA-MAA copolymer has the BMA:MAA monomer ratio of about 90:10.According to an aspect, described BMA-MAA copolymer has the BMA:MAA monomer ratio of about 95:5.

In some embodiments, described high molecular (methyl) acrylate polymer or copolymer have the molecular weight between 1,000g/mol and 20,000g/mol.In some embodiments, described high molecular (methyl) acrylate polymer or copolymer have the molecular weight of at least 2,000g/mol.In some embodiments, described high molecular (methyl) acrylate polymer or copolymer have the molecular weight of at least 3,000g/mol.

In some embodiments, described high molecular (methyl) acrylate polymer or copolymer have the molecular weight between 2,000g/mol and 10,000g/mol.

In some embodiments, described high molecular (methyl) acrylate polymer or copolymer have the molecular weight between 3,000g/mol and 10,000g/mol.

Carbamate (methyl) acrylate

According to some embodiments, the finger paint of present embodiment also can comprise carbamate (methyl) acrylate.Although the compositions of present embodiment can comprise urethane acrylate, urethane methacrylate is preferred, because compared with acrylate formulations, urethane methacrylate is more impossible causes sensitization of skin.Term as used in this article " carbamate (methyl) acrylate " means urethane methacrylate, urethane acrylate or its mixture.

In some embodiments, described carbamate (methyl) acrylate has the molecular weight between 200g/mol and 20,000g/mol.In some embodiments, described carbamate (methyl) acrylate has the molecular weight of at least 2,000g/mol.In some embodiments, described carbamate (methyl) acrylate has the molecular weight of at least 3,000g/mol.In some embodiments, described carbamate (methyl) acrylate has the molecular weight between 2,000g/mol and 10,000g/mol.In some embodiments, described carbamate (methyl) acrylate has the molecular weight between 3,000g/mol and 10,000g/mol.

In some embodiments, described carbamate (methyl) acrylate is the urethane methacrylate of aliphatic polyol modification.Such molecule can by comprise aliphatic polyol, hydroxyalkyl methacrylate and vulcabond and have the reactant of the weight average molecular weight of scope such as about 1000 to about 6000 reaction formed.The also known method manufacturing polyalcohol modified urethane methacrylate when not using vulcabond.In some embodiments, described aliphatic polyol is polyethers, polyester, polybutadiene and/or Merlon.

Such as, in some embodiments, described carbamate (methyl) acrylate is the urethane methacrylate based on aliphatic polyester polylol.Such molecule can by comprise aliphatic polyester polylol, hydroxyalkyl methacrylate and vulcabond and have the reactant of the weight average molecular weight of scope such as about 1000 to about 6000 reaction formed.

In some embodiments, described hydroxyalkyl methacrylate is selected from hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, methacrylate, methacrylic acid hydroxy pentane ester, the own ester of hydroxyethyl methacrylate and its combination, and more preferably, described hydroxyalkyl methacrylate is hydroxyethyl methylacrylate.

In some embodiments, described vulcabond is selected from isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride diisocyanate, 1-hexahydrotoluene-2,4-vulcabond, dicyclohexyl dimethyl-methane p, p'-vulcabond and its combination.More preferably, described vulcabond is isophorone diisocyanate.

In some embodiments, described carbamate (methyl) acrylate can be polyester, polyethers, polybutadiene and/or polycarbonate urethane oligomer (methyl) acrylate.

In some embodiments, described carbamate (methyl) acrylate is polyether urethane oligomer (methyl) acrylate.Polyether urethane oligomer (methyl) acrylate refers to the compound such as containing at least polyethers, carbamate and (methyl) acrylate group.

In some embodiments, described carbamate (methyl) acrylate is polyester urethane oligomer (methyl) acrylate.Polyester urethane oligomer (methyl) acrylate refers to the compound such as containing at least polyester, carbamate and (methyl) acrylate group.

In some embodiments, described carbamate (methyl) acrylate is polybutadiene oligourethane (methyl) acrylate.Polybutadiene oligourethane (methyl) acrylate refers to the compound such as containing at least polybutadiene, carbamate and (methyl) acrylate group.

In some embodiments, described carbamate (methyl) acrylate is polycarbonate urethane oligomer (methyl) acrylate.Polycarbonate urethane oligomer (methyl) acrylate refers to the compound such as containing at least Merlon, carbamate and (methyl) acrylate group.

Due to as follows, these oligourethanes (methyl) acrylate is facile: make polyester, polyethers, polybutadiene and/or PCDL (diol component) are with aliphatic, alicyclic and/or aromatic diisocyanates such as 1, 6-hexamethylene diisocyanate (HDI), 2, 4, 4-tri-methyl hexamethylene-1, 6-vulcabond (TMDI), tetramethylene diisocyanate, isophorone diisocyanate, 4, 4 '-dicyclohexyl methyl hydride diisocyanate, 1, 4-phenylene vulcabond, 2, 6-and 2, 4-toluene di-isocyanate(TDI), 1, 5-naphthalene diisocyanate, 2, 4 '-and 4, 4 '-methyl diphenylene diisocyanate (diisocyanate component) reacts under amine or stannum catalysis.If use the diol component of molar excess compared with diisocyanate component thus, then residual terminal OH groups, its available ethylenic unsaturated acid is as acrylic acid or the esterification of one of methacrylic acid or their derivant.If use the diisocyanate component of molar excess compared with diol component, then residual terminal isocyanate group group, itself and hydroxyalkyl and/or hydroxyaryl (methyl) acrylate and/or two (methyl) acrylate and/or three (methyl) acrylate such as acrylic acid 2-hydroxy methacrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), methacrylic acid 3-hydroxy propyl ester (HPMA), acrylic acid 3-hydroxy propyl ester (HPA), glycerine dimethacrylate and/or glycerol diacrylate react.

Available polycarbonate polyol be such as by with glycol as 1, ammediol, 1,4-butanediol, 1,6-hexanediol, diglycol, neopentyl glycol, trimethyl-1,6-hexanediol, 3-methyl isophthalic acid, 5-pentanediol and/or tetraethylene-glycol, with diaryl carbonate as dipheryl carbonate base ester or the product be obtained by reacting with phosgene.

Available polyether polyol comprise such as by the polymerization of cyclic oxide such as oxirane, expoxy propane or oxolane or by one or more and Multifunctional initiator of these oxides as the addition of water, ethylene glycol, propylene glycol, diglycol, cyclohexanedimethanol, glycerol, trimethylolpropane, tetramethylolmethane or bisphenol-A facile product.The polytetramethylene ether diol that particularly suitable polyether polyol is polyoxypropylene glycol and triol or poly-(oxygen ethylidene-oxygen propylidene) glycol obtained to the addition simultaneously or sequentially of suitable initiator by oxirane or expoxy propane and triol and is produced by the polymerization of oxolane.

In some embodiments, polyethers comprises polyethylene glycol oxide, polypropylene oxide, polyoxybutylene.

In some embodiments, polyester comprises polypropylene glycol, Polyethylene Glycol, polytetramethylene glycol, PEP-101, oxolane-ethylene oxide copolymer, oxolane-epoxy propane copolymer, p-phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid, cyclohexane cyclohexanedimethanodibasic, 1,2-propane diol (propylene glycol), dipropylene glycol, diglycol, 1,3 butylene glycol, ethylene glycol and glycerol.

Transmit strengthen adhesion and give polymerization grid with the polymer of solvent sensitivity

Some embodiment of described fluid composition comprises the such polymer of at least one: it is introduced in 3-D grid and it transmits the adhesion and its grid giving polymerization that strengthen with solvent sensitivity.In the existence of polymer/some polymer of fingernail interface, interface cohesion is easily destroyed by organic solvent.

According to an aspect, not only transmit the adhesion of enhancing but also make the polymer of polymer/nail surface to solvent-susceptible be the copolymer of polymethyl methacrylate and polymethylacrylic acid.According to an aspect, described monomer is present in described polymer the ratio (90:10PMMA:PMAA) of 10 parts of PMAA with 90 parts of PMMA.According to an aspect, PMAA monomer fraction can from 0 to 100% change.According to an aspect, described PMMA-PMAA copolymer has the PMMA:PMAA monomer ratio of about 50:50.According to an aspect, described PMMA-PMAA copolymer has the PMMA:PMAA monomer ratio of about 60:40.According to an aspect, described PMMA-PMAA copolymer has the PMMA:PMAA monomer ratio of about 80:20.According to an aspect, described PMMA-PMAA copolymer has the PMMA:PMAA monomer ratio of about 90:10.According to an aspect, described PMMA-PMAA copolymer has the PMMA:PMAA monomer ratio of about 95:5.

Some embodiment of described fluid composition comprises gives described interface cohesion with at least one monomer of the high sensitivity level to organic solvent.According to an aspect, described at least one monomer can be polypropylene glycol-4-monomethacrylates (PPG-4 monomethacrylates) or polypropylene glycol-5-monomethacrylates (PPG-5 monomethacrylates).According to an aspect, the monomer in Polyethylene Glycol (PEG), polypropylene glycol (PPG) or polytetramethylene glycol (PBG) family that is that suitable monomer can comprise any acroleic acid esterification or methacrylated.According to an aspect, such monomer exists with about 0-about 70 % by weight (wt%).

In some embodiments, the described interface cohesion of described imparting can be polyalcohol modified carbamate (methyl) acrylate with the monomer of the high sensitivity level to organic solvent.

In some embodiments, described finger paint compositions that is removable, promotion adhesion (power) comprises such monomer and oligomer further: it is selected such that the various keys in gained thermosets are endowed the sensitivity to solvent of raising.In some embodiments, such monomer and oligomer are selected from propoxylation allkyl methacrylate, methoxy poly (ethylene glycol) (350) monomethacrylates, Polyethylene Glycol (600) monomethacrylates, stearyl methacrylate, Tridecyl methacrylate base ester, hydroxyethyl meth acrylate acetas and its mixture.

Carbamate (methyl) acrylate

Some embodiment of the fluid composition that can be polymerized of present disclosure can comprise and can transmit carbamate (methyl) acrylate that is flexible and toughness to the product of polymerization.In some embodiments, urethane methacrylate is preferred.Described carbamate (methyl) acrylate monomer can exist by about 0-about 80 % by weight.In some embodiments, described carbamate (methyl) acrylate can have the molecular weight (gram/mol) of from about 100 to about 20,000.In some embodiments, described carbamate (methyl) acrylate can have the molecular weight of from about 300 to about 15,000.In some embodiments, described carbamate (methyl) acrylate can have the molecular weight of from about 500 to about 13,000.In some embodiments, described carbamate (methyl) acrylate can have the molecular weight of from about 500 to about 6,000.

(methyl) acrylate monomer of the adhesion of improvement, viscosity, wearing and tearing and durability is provided

An embodiment of present disclosure provides the fluid composition that can be polymerized be made up of (methyl) acrylate monomer of the adhesion providing improvement, viscosity, wearing and tearing and durability.In some embodiments, described (methyl) acrylic monomers is tetrahydrofurfuryl methacrylate.In other embodiment, some or all of described tetrahydrofurfuryl methacrylate can be replaced by such monomer: it includes, but are not limited to methyl methacrylate or ethyl methacrylate, Hydroxypropyl methacrylate or methacrylate and/or other monomer such as pyromellitic acid anhydride glyceryl dimethylacrylate and similar (methyl) acrylate monomer.Aromatics or aliphatic series (methyl) acrylate monomer can exist by about 0-about 70 % by weight.

The aromatics or aliphatic series (methyl) acrylate monomer that improve adhesion can be there is

Some embodiment of present disclosure can comprise other aromatics or aliphatic series (methyl) acrylate monomer that can there is to improve adhesion.Described (methyl) acrylate monomer can be pyromellitic acid anhydride glyceryl dimethylacrylate (PMGDM).Usually, this methacrylate monomer can be sour functionality (methyl) acrylate monomer.(methyl) acrylate monomer of described sour functionality can be carboxylic acid polyalcohol.This methacrylate monomer can exist by about 0-about 70 % by weight.

Free oh group

Compositions of the present invention comprises the monomer and oligomer with multiple free hydroxyl radicals.The oh group of the present composition for the substrate that can be keratin protein nail surface formed can be for hydrogen bond available.The oh group of the present composition for the substrate with the surface that can be natural nail or artificial nails's reinforce coating formed can be for hydrogen bond available.

Adhesion promoter (being different from POSS)

Described some embodiment removable, that promotion adheres to the finger paint compositions of (power) can also comprise adhesion promoter except POSS.Described extra adhesion promoter can be selected from Hydroxypropyl methacrylate (HPMA), hydroxyethyl methylacrylate (HEMA), ethyl methacrylate (EMA), tetrahydrofurfuryl methacrylate (THFMA), pyromellitic acid anhydride two (methyl) acrylate, pyromellitic acid anhydride glyceryl dimethylacrylate, Pyromellitic Acid dimethylacrylate, methyl acryloyloxyethyl isocyanate, 2-HEMA/succinate, 1,3-glycerine dimethacrylate/succinate adduct, methacrylic acid phthalic acid list ethyl ester, methyl acryloyloxyethyl isocyanate, 2-HEMA/succinate, 1,3-glycerine dimethacrylate/succinate adduct, butyl methacrylate, isobutyl methacrylate, PEG-4 dimethylacrylate, PPG monomethacrylates, trimethylol-propane trimethacrylate, isopropylidene diphenyl 2-glycidyl methyl acrylate, lauryl methacrylate, cyclohexyl methacrylate, N-Hexyl methacrylate, urethane methacrylate, triethylene-glycol dimethylacrylate, ethylene glycol dimethacrylate, tetraethylene-glycol dimethylacrylate, trimethylol-propane trimethacrylate, neopentylglycol dimethacrylate, acetoacetoxy groups methacrylate, acetoacetoxyethyl methacrylate (AAEMA), polyetheramine, glycidyl methacrylate, maleic anhydride, terpolymer containing vinyl acetate, organosilan, organic titanate, chloridized polyolefin, sucrose acetate isobutyrate, caprylic/capric triglyceride, hydrogenated rosins acid glyceride, hydrogenated rosins acid pentaerythritol ester, styrene/methyl styrene/indene copolymer, the isocyanates PVC of end-blocking, daiamid PVC, with its mixture.

The polymer (film former) non-reacted, solvent can be dissolved in

Some embodiment of the fluid composition that can be polymerized of present disclosure can comprise non-reacted, to be dissolved in solvent polymer.According to an aspect, described polymer that is non-reacted, that can be dissolved in solvent is cellulose esters.According to a concrete aspect, described polymer that is non-reacted, that can be dissolved in solvent is cellulose ethanoate alkylates.According to an aspect more specifically, described polymer that is non-reacted, that can be dissolved in solvent is cellulose acetate-butyrate or cellulose-acetate propionate.Described non-reacted, mixture that polymer that is that can be dissolved in solvent can be any acceptable polymer.According to a further aspect, described polymer that is non-reacted, that can be dissolved in solvent can exist with about 0-about 75 % by weight.

Describedly to remove, promote that the finger paint compositions adhering to (power) can be following non-reacted containing being selected from, the polymer of solvent can be dissolved in: ethyl toluenesulfonamide, adipic acid/fumaric acid/phthalic acid/Tricyclodecane Dimethanol copolymer, adipic acid/neopentyl glycol/trimellitic acid anhydride copolymer, phthalic anhydride/trimellitic anhydride/(second) diol copolymer, poly-ethyl cellulose, poly-hydroxypropyl cellulose, polyethyl acrylate oxide, polylactic acid, nitrocellulose, cellulose esters, with its mixture.

Optional resin (one or more)

Some embodiment of described formula optionally can contain resin, and described resin is such as, but not limited to, polyvinyl butyral resin and/or tosyl amine-formaldehyde resins.These resins can serve as film former, adhesion promoter, and help to remove.These resins are also qualified as such resin that can be dissolved in solvent: its to be dispersed in the structure of polymerization and can easily by dissolution with solvents to promote solvent absorption and migration during removal.

Plasticizer

Compositions of the present invention can contain the plasticizer from about 0.001 % by weight to about 20 % by weight.Compositions of the present invention can containing from about 0.01 % by weight to about 15 % by weight, from about 0.05 % by weight to about 10 % by weight, from about 0.1 % by weight to about 5 % by weight or from about 0.5 % by weight to about 2 % by weight plasticizer.Described plasticizer causes the nail structure be polymerized to have the flexibility of improvement and the fragility of reduction.Suitable plasticizer can be that ester, low voc solvent or non-ionic materials are as nonionic organic surface active agent or organosilicon.

In some embodiments, describedly to remove, promote that the finger paint compositions adhering to (power) contains further from about 0.001 % by weight to about 20 % by weight, from about 0.01 % by weight to about 15 % by weight, from about 0.05 % by weight to about 10 % by weight, from about 0.1 % by weight to about 5 % by weight, or from about 0.5 % by weight to about 2 % by weight be selected from following plasticizer: ester, low voc solvent (paraffin hydrocarbon, butyrolactone, dimethylbenzene, methyl iso-butyl ketone (MIBK)), nonionic surfactant, non-ionic silicone, different n-nonanoic acid iso stearyl ester, organosilicon, diisobutyl adipate, tri-methyl-amyl diisobutyrate, acetyl tributyl citrate, with its mixture.

Suitable ester comprises those with general structure RCO--OR', and wherein RCO-represents hydroxy-acid group and wherein-OR' is alcohol residue.Preferably, R and R' is the aliphatic group with 6-30 carbon atom, and can be saturated or unsaturated.The example of suitable ester is at C.T.F.A.CosmeticIngredientDictionaryandHandbook, SeventhEdition, the 1558-1564 page of 1997 is set forth those, it is incorporated herein by reference thus.In preferred composition of the present invention, described plasticizer is the ester of formula RCO--OR', and wherein R and R' is straight or branched C independently of one another _6-30alkyl.Suitable plasticizer is different n-nonanoic acid iso stearyl ester.Other suitable plasticizer is open in U.S. Patent No. 6818207, is introduced into as a reference.

UV stabilizing agent

According to some embodiment, described formula may further include at least one UV stabilizing agent.In some embodiments, described UV stabilizing agent exists to be up to 2 % by weight.

Compositions of the present invention can contain one or more UV absorbent, and it is assisted and reduces yellow common in artificial nails.It is the ability of less destructive infra-red radiation (heat) or visible ray that UV absorbent has the UV converts radiation of incidence.The recommended amounts of UV absorbent is the 0.001-5% weight of whole compositions.Suitable UV absorbent comprises hydroxybenzotriazole compound and benzophenone compound, disclosed in U.S. Patent No. 6818207, is introduced into as a reference.

Describedly to remove, promote to adhere to (power) finger paint compositions can containing be up to 5 % by weight be selected from following UV absorbent: hydroxybenzotriazole compound is as 2-(2-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, benzophenone, 1-12, Unisol S-22, benzyl salicylate, Borneolum Syntheticum ketone, Borneolum Syntheticum, Camphora, bumetrizole, PABA, butyl PABA, PAROSOL 1789, cinoxate, DEA-methoxycinnamate hydrochlorate, dibenzo azoles base naphthalene, digalloyl trioleate (digalloyltrioleate), diisopropyl methyl cinnamyl acid esters with its mixture.

Polymerization/light trigger

Some embodiment of the disclosed compositions that can be polymerized can be gel or the liquid of viscosity.Gel or liquid embodiment can be polymerized by being exposed to emittance such as heat, visible ray, UV or electron beam irradiation.Liquid or gel embodiment to be applied on fingernail and the configuration of needs can be configured as.The fingernail of coating is exposed to polymerization initiator such as emittance, or chemical polymerisation initiator is comprised as peroxide or in formula as described in being mixed into, and polymerization occurs.

Compositions of the present invention can be is polymerized with photochemical radiant energy.Described actinic radiation can be visible ray, ultraviolet (UV) or electron beam irradiation.Described UV radiation can be characterised in that typically but be not limited to about 320 nanometers to the wavelength of about 420 nanometers or set of wavelengths.

After described fluid composition is applied to nail surface, described liquid polymeric or solidification.Described fluid composition comprises olefinic unsaturated (methyl) acrylate, the free radical polymerisation process polymerization that it can be caused by UV or solidification.The technical staff of polymerization field can easily determine to use and stark suitable light trigger for together with the present invention.Suitable light trigger includes, but not limited to benzoyl diphenyl phosphinate, phenyl ketone and dimethyl ketal.What set forth below is the nonrestrictive representative light trigger being suitable for the invention is intended to.

Nonrestrictive suitable light trigger is 2,4,6-trimethyl benzoyl diphenyl base phosphorus derivant.Suitable derivant is ethyl-2,4,6-trimethyl benzoyl diphenyl base phosphinate, and it can with trade name tPO-L (BASFAktiengesellschaft, Ludwigshafen, DE) obtains.Another nonrestrictive suitable derivant is 2,4,6-trimethylbenzoyldiphenyl oxide, and it can with trade name tPO (BASF) or conduct tPO (Rahn) obtains.2,4,6-trimethyl benzoyl diphenyl base phosphinate light trigger can exist with about 0%-20 % by weight.

Nonrestrictive suitable light trigger is hydroxycyclohexylphenylketone, and it can with trade name 184 obtain and its can exist with about 0-about 20 % by weight.

Nonrestrictive suitable light trigger is dibenzoyl dimethyl ketal (BDK), and it can with trade name bDK (Albemarle, BatonRouge, LA, US) obtains, and it can exist with about 0 to about 20 % by weight.

Polymerization regulator

Comprising one or more polymerization regulators can be desirable.Polymerization regulator assists the polymerization preventing monomer composition too fast to occur.Hydroquinone and similar material are suitable polymerization regulators.The polymerization regulator scope of suggestion is the about 0.0001-5% weight of whole compositions.Suitable polymerization regulator is disclosed in U.S. Patent No. 6818207, is introduced into as a reference.

Color layers/coloring agent

An aspect of present disclosure provides color layers.Some embodiment of color layers can comprise the pigment and/or the dyestuff that are up to 10 % by weight.The embodiment of prime coat layer and face coat can have the pigment and/or the dyestuff that are up to 1 % by weight.The pigment of high concentration and/or dyestuff can absorb UV radiation.Therefore in order to compensate, some embodiment of present disclosure can contain higher concentration, be up to the light trigger of 20 % by weight.

Solvent

Conventional thermosetting finger paint contains 100% solid and does not contain non-reactive solvent.The fluid composition that can be polymerized of present disclosure is further containing at least one non-reactive solvent.Suitable non-reactive solvent is at room temperature volatile and is the good solvent that residue is prepared burden.When applying, described non-reactive solvent easily volatilizees, and leaves the region increasing porosity at finger paint everywhere.These porous zone promote entering of remover solvent subsequently, and described remover solvent can be acetone.

Suitable non-reactive solvent can be selected from ketone, alkyl acetate, alcohol, alkane, alkene and its mixture.Suitable solvent can be selected from acetone, ethyl acetate, butyl acetate, isopropyl alcohol, ethanol, methyl ethyl ketone, toluene, hexane and its mixture.Specially suitable solvent is acetone.Typically, to be up to the mixture that about 70 % by weight comprise solvent or solvent.

Embodiment

Understand, the amendment of the behavior not affecting various embodiment of the present invention in essence is also provided in the definition of the present invention provided in this article.Therefore, the following examples are intended to illustrate instead of limit the present invention.Although the detailed description of the invention in detail and with reference to invention required for protection describes invention required for protection; but those of ordinary skill in the art are by distinct, variations and modifications can be carried out to scope required for protection when not deviating from the spirit and scope of invention required for protection.Therefore, such as, those skilled in the art only use normal experiment just to will appreciate that, maybe can determine, many equivalents of concrete material described herein and program.Such equivalent is deemed to be within the scope of the present invention, and is overwritten by the appended claims.

Embodiment 1:

In one embodiment, prime coat layer finger paint compositions can contain component below:

Preparation adds the exemplary transparent finger paint according to above formula of the POSS added, and test is also compared with control sample (POSS do not added).Control sample corresponds to commercial clear fingernail glaze.

Use and draw the adhesion that lattice adhesion test (CrossHatchAdhesiontest) (ASTMD3359) tests above compositions.Briefly, a stroke grid pattern is produced through described film to described substrate.The paint flakes come off is removed by brushing with soft brush.Pressure Sensitive Tape is applied to described drawing above lattice cut substrate (cut).Described adhesive tape is made smoothly to enter position by using Eraser with pencil holder to wipe at otch (incision) over.By as follows adhesive tape being removed: it is pullled close to the angle of 180 ° in face on itself backward fast.The grade of 0 to 5 assesses adhesion.Following table summarizes the result of self-test.

Formula #	Average adhesion score	Relative to the improvement of control sample
			1	3.0	71％
1 control sample	1.75	-
			2	2.25	125％
2 control samples	1.0	-

Adhesion is measured to this formula with to the same recipe of the POSSEP0409 being added with variable quantity.

POSS	Average adhesion score
		0 % by weight	3.17
2 % by weight EP0409	3.67
		4.67 % by weight EP0409	4.25
10 % by weight EP0409	4.5

Embodiment 2

In another illustrative embodiments, advantageously can add and have the prime coat layer finger paint compositions of POSS to have following component:

Embodiment 3:

To the prime coat layer compositions containing coloring agent, HEMA, HPMA, two-HEMA trimethyl carbamates and hydroxycyclohexylphenylketone with to adding the ethyl acetate having 1:1: the mixture of POSS measures adhesion with the same recipe obtaining 10 % by weight POSS in end formulation.

POSS	Average adhesion score
		0％	1.67
10 % by weight EP0409	4.17
		10 % by weight AM0281	4.00
10 % by weight NB1038	4.83
		10 % by weight PM1285MV	2.17

Embodiment 5:

Adhesion is measured to the prime coat layer formula containing following component: coloring agent, HEMA, HPMA, isobornyl methacrylate, two HEMA trimethyl carbamates, benzophenone, hydroxycyclohexylphenylketone, TPO, trimethylpentane two base diisobutyrate (TrimethylPentarylDiisobutyrate), Camphora, polydimethylsiloxane (dimethicone), nitrocellulose, toluenesulfonamide/epoxy resin, polyvinyl butyral resin, butyl acetate, (second) alcohol, and heptane.To described formula and to adding the ethyl acetate having 1:1: POSS mixture measures adhesion with the same recipe obtaining 10 % by weight POSS in end formulation.

Embodiment 6

With the same recipe obtaining 10 % by weight POSS in end formulation, adhesion is measured to adding the HEMA:POSS mixture having 1:1 to the prime coat layer formula of embodiment 5.

POSS	Average adhesion score
		0 % by weight	3.83
10 % by weight PM1258MV	4.50

Embodiment 7:

In an illustrative embodiments, advantageously can add and have the color layers finger paint compositions of POSS to have following component:

Embodiment 8:

To the color layers formula of embodiment 7 with to the same recipe measurement adhesion with 10 % by weight POSSNB1038.Battery of tests (left hurdle) uses 1 coating, solidification in 4 minutes, IPA wiping.Second group (right hurdle) uses 2 coatings, solidification in 4 minutes, IPA wiping.

Embodiment 9

To the color layers formula containing following component with to adding the ethyl acetate having 1:1: POSS mixture measures adhesion with the same recipe obtaining 10 % by weight POSS in end formulation: oronain hectorite draws in department, coloring agent, HEMA, HPMA, isobornyl methacrylate, two HEMA trimethyl carbamates, hydroxyl cyclohexyl methyl phenyl ketone, citric acid, polydimethylsiloxane (plasticizer), phosphoric acid, nitrocellulose, butyl acetate, diacetone alcohol, and ethyl acetate.

POSS	Average adhesion score
		0％	0
10 % by weight NB1038	0.50
		10 % by weight AM0281	0.50

Embodiment 10:

To the color layers formula containing following component and to adding the THFEMA:POSS mixture of HEMA:POSS mixture or the 1:1 having 1:1 to obtain the same recipe measurement adhesion of 10 % by weight POSS in end formulation: coloring agent, HEMA, HPMA, two HEMA trimethyl carbamates, benzophenone-1, diphenyl-2,4-trimethylbenzoyl phosphinic acid, polydimethylsiloxane, polysiloxanes (Polysilicone)-13, PEG-2 polydimethylsiloxane and synthetic wax.

POSS	Average adhesion score
		0％	0.83
10 % by weight NB1038/THFMA	2.83

Embodiment 11:

By using Hesiometer to analyze, measure peak strength and the peel strength of liquid-and-powder finger paint.Sample is tested on RomulusIIIAHesiometer.Arrange method of testing, each test is allowed, and the blade arranged in order to 15 ° of angles is advanced 4.5mm while applying 10 Newton force to substrate.Data are obtained by the figure of power to displacement.In order to determine the data point of peak value or impact strength, take the integration at primary data peak.In order to determine the data point of stripping or adhesion strength, take the integration of the platform (plateau) from 2.5mm to 4.5mm.

The test peak value display carried out or impact strength increase substantially along with the interpolation of glycidyl POSS.After the inspection of sample, the reduction of peel strength may be the result of the leafing (it can affect peel strength measurement result) of the coating before blade that the strength owing to applying during peak strength measurement causes.

Embodiment 12:

To a series of glaze based on water and to adding the same recipe measurement adhesion having POSS (EP0409).The glaze based on water used comprises following commercially available prod: water, styrene-acrylic copolymer emulsion, acrylate copolymer emulsion and coloring agent.POSS directly joins these formula with the level of 1% and 5%.

POSS	Average dry adhesion score	Average wet adhesion score
			0％	2.5	0.17
1％POSS	4.25	1.33
			5％POSS	3.67	1.50

Other embodiment within the scope of the appended claims.

Claims (20)

1. finger paint compositions, it contains:

At least one polyhedral oligomeric silsesquioxane; With

At least one reactive monomer, oligomer or polymer.

2. the finger paint compositions of claim 1, wherein said at least one polyhedral oligomeric silsesquioxane is selected from: glycidyl POSS clathrate compound mixture (EP0409); Trimethoxy-[2-(7-oxabicyclo [4.1.0]-3-in heptan base) ethyl] silane, (EP0408) of hydrolysis; [3-(trimethoxysilyl) propyl group] aniline (AM0281) of hydrolysis; [(dimethyl (norbornenylethyl) siloxy) dihydroxy]- (NB1038); Vinyl silsesquioxane resin-liquid state (PM1285MV); Acrylo clathrate compound mixture (MA0736); The ethoxylation POSS of methacrylated; The glycidyl POSS of ethoxylation; Or its mixture.

3. the finger paint compositions of claim 1, wherein said at least one polyhedral oligomeric silsesquioxane is glycidyl POSS clathrate compound mixture (EP0409).

4. the finger paint compositions of claim 1, wherein said reactive monomer, oligomer or polymer are reactive (methyl) acrylate.

5. the finger paint compositions of claim 4, wherein said reactivity (methyl) acrylate is selected from: Hydroxypropyl methacrylate (HPMA), hydroxyethyl methylacrylate (HEMA), ethyl methacrylate (EMA), tetrahydrofurfuryl methacrylate, pyromellitic acid anhydride two (methyl) acrylate, pyromellitic acid anhydride glyceryl dimethylacrylate, Pyromellitic Acid dimethylacrylate, methyl acryloyloxyethyl isocyanate, 2-HEMA/succinate, 1, 3-glycerine dimethacrylate/succinate adduct, methacrylic acid mono-ethyl phthalate, or its mixture.

6. the finger paint compositions of claim 1, it is further containing film forming polymer or the non-reacted polymer that can be dissolved in solvent.

7. the finger paint compositions of claim 6, wherein said can be dissolved in solvent polymer or film forming polymer be selected from: cellulose esters, cellulose ethanoate alkylates, cellulose acetate-butyrate, cellulose-acetate propionate, ethyl toluenesulfonamide, adipic acid/fumaric acid/phthalic acid/Tricyclodecane Dimethanol copolymer, adipic acid/neopentyl glycol/trimellitic acid anhydride copolymer, phthalic anhydride/trimellitic anhydride/glycol copolymer, poly-ethyl cellulose, poly-hydroxypropyl cellulose, polyethyl acrylate oxide, polylactic acid, nitrocellulose, cellulose esters, with its mixture.

8. the finger paint compositions of claim 7, wherein said can be dissolved in solvent polymer or film forming polymer be high molecular (methyl) acrylate polymer or copolymer.

9. finger paint compositions according to claim 7, wherein said can be dissolved in solvent polymer or film forming polymer be polymethyl methacrylate (PMMA)-polymethylacrylic acid (PMAA) copolymer.

10. the finger paint compositions of claim 1, it is further containing solvent.

The finger paint compositions of 11. claim 10, wherein said solvent is nonaqueous solvent.

The finger paint compositions of 12. claim 10, wherein said solvent is water.

Finger paint compositions any one of 13. claim 1-3, it is further containing the reactive polypropylene glycol of at least one (methyl) acrylated monomers or Polyethylene Glycol (methyl) acrylated monomers.

The finger paint compositions of 14. claim 1, it is further containing polymerization accelerator, polymerization initiator or its combination.

Finger paint compositions any one of 15. claim 1-11, it is further containing being selected from following adhesion promoter: Hydroxypropyl methacrylate (HPMA), hydroxyethyl methylacrylate (HEMA), ethyl methacrylate (EMA), tetrahydrofurfuryl methacrylate (THFMA), pyromellitic acid anhydride two (methyl) acrylate, pyromellitic acid anhydride glyceryl dimethylacrylate, Pyromellitic Acid dimethylacrylate, methyl acryloyloxyethyl isocyanate, 2-HEMA/succinate, 1,3-glycerine dimethacrylate/succinate adduct, methacrylic acid phthalic acid list ethyl ester, methyl acryloyloxyethyl isocyanate, 2-HEMA/succinate, 1,3-glycerine dimethacrylate/succinate adduct, butyl methacrylate, isobutyl methacrylate, PEG-4 dimethylacrylate, PPG monomethacrylates, trimethylol-propane trimethacrylate, isopropylidene diphenyl 2-glycidyl methyl acrylate, lauryl methacrylate, cyclohexyl methacrylate, N-Hexyl methacrylate, urethane methacrylate, triethylene-glycol dimethylacrylate, ethylene glycol dimethacrylate, tetraethylene-glycol dimethylacrylate, trimethylol-propane trimethacrylate, neopentylglycol dimethacrylate, acetoacetoxy groups methacrylate, acetoacetoxyethyl methacrylate (AAEMA), polyetheramine, glycidyl methacrylate, maleic anhydride, terpolymer containing vinyl acetate, organosilan, organic titanate, chloridized polyolefin, sucrose acetate isobutyrate, caprylic/capric triglyceride, hydrogenated rosins acid glyceride, hydrogenated rosins acid pentaerythritol ester, styrene/methyl styrene/indene copolymer, the isocyanates PVC of end-blocking, daiamid PVC, with its mixture.

The finger paint compositions of 16. claim 1, wherein said reactive monomer, oligomer or polymer are reactive (methyl) acrylate; And contain the polymer that at least one is non-reacted, can be dissolved in solvent further.

The finger paint compositions of 17. claim 1, wherein said reactive monomer, oligomer or polymer are reactive (methyl) acrylate; And further containing at least one polymethyl methacrylate (PMMA)-polymethylacrylic acid (PMAA) copolymer; The polymer that at least one is non-reacted, can be dissolved in solvent; With at least one non-reactive solvent.

18. methods improving the adhesion of finger paint, it comprises and adds at least one polyhedral oligomeric silsesquioxane to finger paint compositions.

The method of 19. claim 18, wherein said at least one polyhedral oligomeric silsesquioxane is selected from: glycidyl POSS clathrate compound mixture (EP0409); Trimethoxy-[2-(7-oxabicyclo [4.1.0]-3-in heptan base) ethyl] silane, (EP0408) of hydrolysis; [3-(trimethoxy is silica-based) propyl group] aniline (AM0281) of hydrolysis; [(dimethyl (norbornenylethyl) siloxy) dihydroxy]- (NB1038); Vinyl silsesquioxane resin-liquid state (PM1285MV); Acrylo clathrate compound mixture (MA0736); The ethoxylation POSS of methacrylated; The glycidyl POSS of ethoxylation; Or its mixture.

The method of 20. claim 18, wherein said at least one polyhedral oligomeric silsesquioxane is glycidyl POSS clathrate compound mixture (EP0409).